Smoking compositions

ABSTRACT

This invention provides tobacco and non-tobacco smoking compositions which contain a heterocyclic-hydroxy-substituted carboxylate compound as a flavorant additive. 
     In one of its embodiments, this invention provides tobacco compositions which contain a heterocyclic-hydroxy-substituted carboxylic acid flavorant additive such as 2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionic acid: ##STR1## Under smoking conditions the above illustrated heterocyclic-hydroxy-substituted carboxylate additive and its pyrolysis products flavor the mainstream and sidestream smoke.

BACKGROUND OF THE INVENTION

An increasing number of organic materials are being employed asflavoring agents for modifying or improving the flavor and aroma oftobaccos, foodstuffs, beverages and other such consumer products.

The incorporation of flavorants in tobacco products is an importantdevelopment in the tobacco industry due to the lowered aromaticity ofthe available tobacco and the increased preference of smokers for filtercigarettes and low delivery cigarettes.

It has been established that alkylpyrazines are natural components oftobacco smoke, and that they most probably are important contributors totobacco smoke flavor [A. Baggett et al, J. Chromatog, 97, 79 (1974)].Further, it has been disclosed in the patent literature that addition ofalkylpyrazines to tobacco results in an improvement in the flavor ofsmoking compositions as perceived by a test panel.

British 1,244,068 describes a method for influencing the smoke flavor oftobacco or a tobacco mixture which consists of treating the tobacco witha pyrazine derivative of the following chemical structure: ##STR2## inwhich each R is independently a hydrogen atom, an aliphatic radical, analicyclic radical or an aromatic hydrocarbon radical such radicalshaving up to 9 carbon atoms, or R is a heterocycli radical containing 4to 9 carbon atoms.

U.S. Pat. No. 3,402,051 describes a process for imparting a popcorn-likeflavor and aroma to tobacco and foodstuffs by the incorporation of a2-acetylpyrazine derivative therein.

Other patents which disclose the addition of various pyridine andpyrazine compounds to tobacco and foodstuffs as a means of providingflavor or flavor enhancement include U.S. Pat. Nos. 3,684,809;3,705,158; 3,716,543; 3,754,934; 3,764,349; 3,767,426; and 3,881,025.

U.S. Pat. No. 3,914,227 discloses pyridyl and pyrazyl ketones and theiruse in altering the organoleptic properties of tobacco and foodstuffs,and U.S. Pat. No. 4,166,869 discloses acylpyrimidines useful asflavorants for the same type of applications.

Alkylpyridines have also been found to be useful tobacco additives. Asan example, U.S. Pat. No. 3,625,224 describes the use ofmethylpyridines, ethylpyridines and various dialkylpyridines as tobaccoadditives. U.S. Pat. No. 3,381,691 discloses2-methyl-5-isopropylpyridine as a tobacco additive.

It is characteristic of pyridine, pyrazine, pyrimidine and otherheterocyclic derivatives employed as tobacco flavorants in the priorart, as illustrated by the above described technical literature, thatthe respective heterocyclic derivatives have the disadvantage of bothhigh volatility and low odor threshold. Both of these propertiessignificantly restrict the extent that these heterocyclic derivativescan be utilized as flavorants in tobacco compositions. A quantity of apyrazine or pyridine derivative in a tobacco composition sufficient tohave a noticeable effect in low delivery cigarettes causes a marked packaroma.

In a similar manner, the use of carboxylic acid flavorants for tobaccoproducts has received acceptance because of the desirable aroma andflavor characteristics which they impart to the smoke (J. C.Leffingwell, H. J. Young, and E. Bernasek, "Tobacco Flavoring forSmoking Products," R. J. Reynolds Tobacco Company, Winston-Salem, 1972).Specifically, acetic acid is commonly used as an ingredient of a Latakiatobacco flavoring formulation (J. Merory, "Food Flavorings," AVIPublishing Company, Incorporated, Westport, Connecticut, page 420,1968). Isovaleric acid and 3-methylvaleric acid are major ingredients ina Turkish tobacco flavor formulation (R. H. Stedman and C. D. Stills,U.S. Pat. No. 3,180,340). Desirable flavors have been imparted tocigarette smoke by the addition of 4-ketoacids to tobacco (W. A. Rohde,U.S. Pat. No. 3,313,307).

Numerous methods of adding flavorants to tobacco smoke are known.However, none of the known methods has been found to be completelysatisfactory, particularly when the flavorant is a low molecular weightcarboxylic acid. Specifically, some of these acids are highly volatileand possess objectionably strong odors that render them difficult to usein bulk amounts required for manufacturing purposes. In addition, someof the volatile acids may impart an undesirable pack aroma.

In an attempt to alleviate some of these problems, carboxylic acids havebeen incorporated in tobacco as part of a compound (i.e., an organicacid release agent) in such form that upon burning of the tobacco thecompound will liberate one or more organic acids imparting a selectedand desired flavor and aroma to the smoke. While considerably moresatisfactory than earlier attempts, even this technique has evidencedcertain drawbacks.

U.S. Pat. No. 2,766,145 through U.S. Pat. No. 2,766,150 describe avariety of methods for treating tobacco with compounds that releasecarboxylic acids on pyrolysis. The U.S. Pat. No. 2,766,145 patentdescribes esters of monohydric and polyhydric compounds. The hydroxycompounds may be aliphatic or aromatic in nature.

The U.S. Pat. No. 2,766,146 describes esters of a sugar acid selectedfrom aldonic acids and uronic acids. U.S. Pat. No. 2,766,150 describesnonvolatile synthetic polymers or condensation products preferably thoserelated to polyvinyl alcohol and vinyl alcohol-type condensationproducts. On pyrolysis, the carboxylic acid is liberated to flavor thesmoke. These polymers have a distinct disadvantage in that theygenerally have high molecular weights and are more difficult tosolubilize for application on tobacco.

Other references which disclose tobacco flavorant compositions thatrelease carboxylic acids on pyrolysis include U.S. Pat. No. 4,036,237and U.S. Pat. No. 4,171,702.

There remains a need for smoking compositions with enhanced flavor andaroma that do not exhibit the various disadvantages of prior art smokingcompositions which contain flavorant additives of the types describedabove.

Accordingly, it is a main object of this invention to provide tobaccoand non-tobacco smoking compositions which have incorporated therein aflavorant additive which is characterized by low volatility and low packaroma.

It is another object of this invention to provide smoking compositionsof tobacco and non-tobacco materials, and blends thereof, containing aheterocyclic-hydroxy-substituted carboxylate flavorant additive, whichsmoking compositions are adapted to impart flavor and aroma to themainstream and sidestream smoke under smoking conditions.

It is a further object of this invention to provide novelheterocyclic-hydroxy-substituted carboxylate compounds which can besubjected to pyrolysis conditions to release heterocyclic and carboxylicconstituents which can enhance the flavor and aroma of smokingcompositions and foodstuffs.

Other objects and advantages of the present invention shall becomeapparent from the accompanying description and examples.

DESCRIPTION OF THE INVENTION

One or more objects of the present invention are accomplished by theprovision of a smoking composition which comprises an admixture of (1)combustible filler selected from natural tobacco, reconstituted tobacco,non-tobacco substitutes and mixtures thereof, and (2) between about0.00001 and 2 weight percent, based on the total weight of filler, of aheterocyclic-hydroxysubstituted carboxylic acid compound correspondingto the formula: ##STR3## wherein X is a heterocyclic substituentcontaining between about 2-12 carbon atoms, and any heteroatom in X isselected from oxygen, nitrogen and sulfur; R is a substituent selectedfrom aliphatic, alicyclic and aromatic groups containing between about1-12 carbon atoms; R¹ and R² are hydrogen or substituents selected fromaliphatic, alicyclic and aromatic groups containing between about 1-12carbon atoms, and R¹ and R² when taken together with connecting elementsform an alicyclic structure; or a corresponding salt form of saidcarboxylic acid compound.

Illustrative of the heterocyclic X substituent in the formularepresented above are furyl, tetrahydrofuryl, piperidyl, pyrrolidyl,indyl, pyrazolyl, imidazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl,quinolyl, triazolyl, thienyl, tetrahydrothienyl, thiazyl, and the like,and the same type of heterocyclic structures which contain one or morealkyl groups of about 1-4 carbon atom content.

Preferred heterocyclic X substituents in the formula are those selectedfrom pyrazyl and pyridyl radicals corresponding to the chemicalstructures: ##STR4## where R³ is a substituent selected from hydrogenand C₁₋₄ lower alkyl groups.

Illustrative of the R, R¹ and R² substituents in the formula representedabove are groups which include methyl, ethyl, propyl, butyl, pentyl,hexyl, methoxyethyl, ethoxyethyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, menthyl, furyl , tetrahydrofuryl, piperidyl, pyrrolidyl,pyrazolyl, phenyl tolyl, xylyl, benzyl, phenylethyl, methoxyphenyl,naphthyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, and the like.

As noted previously, R¹ and R² additionally can be hydrogen, and whentaken together with the connecting elements form an alicyclic group suchas cyclopentyl, cyclohexyl, cycloheptyl, menthyl, and the like.

As noted previously, the heterocyclic-hydroxy-substituted carboxylicacid flavorant additive compound can be employed in the form of a salt.The salt is formed by the interaction of the said carboxylic acid withany compound which is sufficiently basic to form a salt with thecarboxylic acid component, and which does not introduce an undesirableoff-flavor, and the like.

Illustrative of salt derivatives are those formed by interaction of thecarboxylic acid with alkali and alkaline earth basic compounds, e.g.,sodium, potassium, lithium and calcium hydroxides and carbonates. Othersalt derivatives are those formed by interaction of the carboxylic acidwith ammonia and organic amines. Typical organic amines include primary,secondary and tertiary aliphatic and aromatic amines such as amylamine,octylamine, dodecylamine, cyclopentylamine, benzylamine, 2-aminobutanol,monoethanolamine, dipropylamine, dibenzylamine, diethanolamine,pyrrolidine, N-methylpyrrolidine, morpholine, piperidine, piperazine,tripropylamine, tributylamine tribenzylamine, triethanolamine, and thelike.

A heterocyclic-hydroxy-substituted carboxylic acid compoundcorresponding to the formula represented above is a low volatilityflavorant which under normal smoking conditions, or other comparablyintensive localized heating conditions, volatilitizes and evolves as agaseous component. Concomitantly, a portion of theheterocyclic-hydroxy-substituted carboxylic acid compound pyrolyzes toyield three separate products which respectively exhibit flavorantproperties. These secondary flavorant compounds are released inaccordance with the following illustrated reaction mechanism: ##STR5##

Similar pyrolysis results are obtained when theheterocyclic-hydroxy-substituted carboxylic acid starting material is inthe form of a salt, except that less of the ethylene secondary flavorantcompound is derived in the pyrolyzate. For example, pyrolysis of a metalcarboxylate salt might yield little or no ethylene flavorant in thepyrolyzate.

It is an important aspect of the present invention that the pyrolysis ofan amine salt can yield up to four secondary flavorant compounds:##STR6## where X, R, R¹ and R² are as previously defined, and Y is abasic organic amine.

Each of the pyrolysis products illustrated above can impart flavor andaroma to tobacco and non-tobacco smoke under smoking conditions.

If it is desirable to produce a large proportion of ethylene compound inthe pyrolyzate, then a free acid form ofheterocyclic-hydroxy-substituted carboxylic acid is employed as thestarting material. As it is apparent, in one of its embodiments thisinvention provides a convenient pyrolysis method for producingheterocyclic-substituted ethylene derivatives corresponding to theformula: ##STR7## wherein X is a heterocyclic substituent containingbetween about 2-12 carbon atoms, and any heteroatom in X is selectedfrom oxygen, nitrogen and sulfur; R is a substituent selected fromaliphatic, alicyclic and aromatic groups containing between about 1-12carbon atoms; R¹ and R² are hydrogen or substituents selected fromaliphatic, alicyclic and aromatic groups containing between about 1-12carbon atoms, and R¹ and R² when taken together with connecting elementsform an alicyclic structure.

Inclusive of the derivatives which can be prepared by the pyrolysismethod is a novel group of heterocyclic-substituted ethylene derivativescorresponding to the formula: ##STR8## wherein X¹ is a heterocyclicsubstituent selected from pyridyl and pyrazyl radicals containingbetween about 2-12 carbon atoms, and R is a C₁ -C₈ alkyl substituent.

Preparation Of Heterocyclic-hydroxy-substituted Carboxylate Compounds

One method of preparing the heterocyclic-hydroxy-substituted carboxylatecompounds of the present invention is by the reaction of a carboxylicacid (or its corresponding salt) with a carbonyl derivative, (e.g.,X--CO--R as previously defined), both of which derivatives areappropriately substituted: ##STR9##

The reaction is conducted in the presence of a strong base such aslithium diisopropylamide, or alkali metal hydride. The strong baseinitiates the in situ formation of a dianion intermediate: ##STR10##

Preferably, the base is added to the carboxylate starting material in aninert solvent medium maintained at a temperature between about -80° and50° C. and under an inert atmosphere. This procedure is followed by theaddition of the heterocyclic-carbonyl compound to the reaction medium ata temperature between about -80° and 25° C.

The resultant heterocyclic-hydroxy-substituted carboxylic acid type ofaddition products obtained above are odorless, normally liquid compoundsof high boiling point. The salt form of the addition products areusually white solids. The salt can be formed by reacting the productwith the appropriate base.

Preparation Of Tobacco Compositions

The present invention smoking compositions can be prepared by admixingnatural tobacco and/or reconstituted tobacco and/or a non-tobaccosubstitute with between about 0.00001 and 2 weight percent, andpreferably 0.0001-2 weight percent, based on the weight of the smokingcomposition, of a flavorant additive which corresponds to one of thestructural formulae set forth hereinabove in definition of theheterocyclic-hydroxy-substituted carboxylate compounds.

The invention heterocyclic-hydroxy-substituted carboxylate flavorantadditive can be incorporated into the tobacco in accordance with methodsknown and used in the art. Preferably the flavorant additive isdissolved in a solvent such as water, alcohol, or mixtures thereof, andthen sprayed or injected into the tobacco or non-tobacco substitutematrix. Such method ensures an even distribution of the flavorantadditive throughout the tobacco, and thereby facilitates the productionof a more uniform smoking composition. Alternatively, the flavorant maybe incorporated as part of a concentrated tobacco extract which isapplied to a fibrous tobacco web as in the manufacture of reconstitutedtobacco. Another suitable procedure is to incorporate the flavorant intobacco or non-tobacco substitute filler in a concentration betweenabout 0.5-5 weight percent, based on the weight of filler, and thensubsequently to blend the treated filler with filler which does notcontain flavorant additive.

The term "non-tobacco substitute" is meant to include smoking fillermaterials such as are disclosed in U.S. Pat. Nos. 3,529,602; 3,703,177;3,796,222; 4,019,521; 4,079,742; and references cited therein;incorporated herein by reference.

Illustratively, U.S. Pat. No. 3,529,602 describes a burnable sheet whichmay be used as a tobacco substitute, which sheet contains ingredientswhich include (1) a film-forming ingredient comprising a pectinaceousmaterial derived from tobacco plant parts and having an acid value inexcess of 30 milligrams of potassium hydroxide per gram, and (2) amineral ingredient comprising an alkali metal salt, an alkaline earthmetal salt or a clay.

U.S. Pat. No. 3,703,177 describes a process for preparing a non-tobaccosmoking product from sugar beet pulp, which process involves the acidhydrolysis of the beet pulp to release beet pectins, and at least analkaline earth treatment thereafter to cause crosslinking of the pectinsand the formations of a binding agent for the exhausted beet matrix.

U.S. Pat. No. 3,796,222 describes a smoking product derived from coffeebean hulls. The hulls are treated with reagents that attack the alkalineearth metal crosslinks causing the release of the coffee pectins. Thepectins act as a binding agent and together with the treated hulls maybe handled and used similarly to a tobacco product.

U.S. Pat. No. 4,019,521 discloses a process for forming a smokingmaterial which involves heating a cellulosic or carbohydrate material ata temperature of 150° -750° C. in an inert atmosphere for a period oftime sufficient to effect a weight loss of at least 60 percent but notmore than 90 percent.

U.S. Pat. No. 4,079,742 discloses a process for the manufacture of asynthetic smoking product from a cellulosic material, which processinvolves a pyrolysis step and a basic extraction step to yield aresultant matrix which has a tobacco-like brown color and has improvedsmoking characteristics.

In another embodiment, the present invention also contemplates theincorporation of one of the heterocyclic-hydroxy-substituted carboxylatecompounds described above into a article of manufacture which is burnedunder controlled conditions within the environment of a human habitat.In particular, the combustible articles contemplated are those such ascandles, room deodorizers, manufactured fireplace fuel, and the like,the burning of which evolves a gaseous effluent which can be sensed byindividuals within olfactory proximity.

As it is apparent, wood logs can also be treated with a solution of aheterocyclic-hydroxy-substituted carboxylate compound prior to ignitionin a fireplace.

The incorporation of between about 0.01 and 10 weight percent of a novelheterocyclic-hydroxy-substituted carboxylate compound of the presentinvention into a candle, for example, can introduce a pleasant aroma orfragrance into a confined living space when the candle is lighted.

In a further embodiment, the present invention provides a method forimproving the flavor of a foodstuff (e.g., a meat-containing ormeat-simulating product) which comprises contacting the foodstuff with anon-toxic gaseous effluent which is generated by the burning of acombustible material (e.g., a solid fuel) having admixed therewithbetween about 0.01 and 10 weight percent, based on the weight ofcombustible content, of a heterocyclic-hydroxy-substituted carboxylatecompound of the present invention. Illustrative of one of theapplications contemplated is the incorporation of theheterocyclic-hydroxy-substituted carboxylate compound in a smoke-housesystem for curing meats. Also, an invention substituted carboxylatecompound can be incorporated in manufactured carbonaceous fuels (e.g.,charcoal briquettes) which are used for broiling raw meat and fishproducts.

As it is apparent, a present invention heterocyclic-hydroxy-substitutedcarboxylate compound can be employed with optimal advantage in anyapplication for adding flavor or enhancing the flavor of a foodstuff inwhich the foodstuff is subjected to a cooking cycle. The substitutedcarboxylate compound can be admixed with or applied to the surface offoodstuffs prior to or during the cooking phase. The substitutecarboxylate compound can be blended with edible solids or liquid tofacilitate its application as a flavorant additive. A blend of betweenabout 0.01 and 10 weight percent of substituted carboxylate compound invegetable oil, for example, is a convenient medium for imparting flavorto foodstuffs in deep-fry operations. The substituted carboxylatecompound can also be incorporated as a flavorant additive in preparedsauces, gravies and dressings. Suitable edible vehicles or carriers fora present invention substituted carboxylate compound include fats andoils such as cottonseed oil, soy bean oil, olive oil, and peanut oil;emulsified fats and oils such as butter and margarine; gums such asguar, locust bean, gum arabic, carrageenen; and the like.

The following examples are further illustrative of the presentinvention. The reactants and other specific ingredients are presented asbeing typical, and various modifications can be derived in view of theforegoing disclosure within the scope of the invention.

EXAMPLE I Preparation Of2-(2-Butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionic acid ##STR11##

To a solution of diisopropylamine (42.5 grams, 0.42 mole) in 400milliliters of anhydrous ether at -78° C., is added under nitrogen withstirring a solution of butyllithium in hexane (182.5 milliliters, 0.42mole). The resulting mixture is stirred at -78° C. for 15 minutes. Asolution of 3-methylvaleri acid (23.2 grams, 0.2 mole) in 250milliliters of ether is added over a period of 20 minutes, keeping thetemperature below -45° C. The mixture is allowed to warm up to roomtemperature and stirred for 3 hours, at which time the formation of theanion is completed.

To the above suspension, cooled to -10° C., is added with stirring asolution of 3-acetylpyridine (24.2 grams, 0.2 mole) in 100 millilitersof ether over a period of 15 minutes. The mixture is allowed to warm upto room temperature and left stirring at room temperature for 16 hours.The mixture is poured with stirring into 500 milliliters of ice-waterand an ether layer separates. The pH of the aqueous layer is adjusted topH 4-5, and then extracted with 5×125 milliliters of methylene chlorideThe combined washes are dried over magnesium sulfate and evaporatedunder reduced pressure to yield 21.6 grams of a brown glossy solid(45.5%). Small amounts of unreacted 3-methylvaleric acid and3-acetylpyridine present in the product are removed under vacuum (0.1 mmHg) at 80° C.

Analysis calculated for C₁₃ H₁₉ NO₃ : C, 65.80; H, 8.07; N, 5.90 ;Found: C, 65.81; H, 8.09; N, 5.89

Employing the same procedure as described above, the followingheterocyclic-hydroxy-substituted carboxylic acid compounds are preparedby the interaction of the appropriately substituted heterocyclic ketonereactant and acid reactant:

2-Cyclohexyl-3-ethyl-3-hydroxy-3-(2-pyridyl)propinoic acid;

2-Methyl-3-hydroxy-3-methyl-3-(2-tetrahydrothienyl)propionic acid;

2,2-Dimethyl-3-hydroxy-3-phenyl-3-(4-pyridyl)propionic acid; and

2-(2-Butyl)-3-hydroxy-3-methyl-3-(2-pyrrolidyl)propionic acid.

EXAMPLE II Preparation Of Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionate ##STR12##

A solution of one gram of hydroxy-acid (Example I) in 25 milliliters ofwater is treated with one equivalent of sodium carbonate and thesolution is stirred for 16 hours. The water is removed under reducedpressure to yield the sodium salt in the form of a white solid.

When the hydroxy-acid starting material is reacted with ammonia or anorganic amine, the corresponding ammonium or amine salt form of thecarboxylate compound is obtained.

Preparation of 2-(2-Butyl)-3-hydroxy-3-methyl-3-(2-pyrazyl)propionicacid ##STR13##

The reaction of 2-acetylpyrazine (21.6 grams, 0.18 mole) with thedianion of 3-methylvaleric acid (from 23.2 grams of acid, 0.2 mole) isconducted in the manner described in Example I, except thattetrahydrofuran is employed as the solvent.

A 31.9 gram quantity of crude product is recovered, and purified as inExample I to yield 14.3 grams of pure product (33.3%).

Analysis calculated for C₁₂ H₁₈ N₂ O₃ : C, 60.48; H, 7.61; N, 11.76;Found: C, 60.77; H, 7.68; N, 12.00

Employing the same procedure as described in Example I, the followingheterocyclic-hydroxy-substituted carboxylic acid compounds are preparedby the interaction of the appropriately substituted heterocyclic ketonereactant and acid reactant:

2,2-Dimethyl-3-hydroxyl-3-(1-naphthyl)-3-(2,3-diethyl-5-pyrazyl)propionicacid;

3-(2-Butyl-3-pyrazyl)-3-hydroxy-3-phenylpropionic acid;

2-(2-Butyl)-3-hydroxy-3-methyl-3-(2-pyrimidyl)propionic acid; and

2-Methyl-3-hydroxy-3-methyl-3-(2-imidazolyl)propionic acid.

EXAMPLE IV Preparation of2-(2-Butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionic acid ##STR14##

The reaction of 4-acetylpyridine (24.1 grams, 0.2 mole) with the dianionof 3-methylvaleric acid (from 23.2 grams of acid, 0.2 mole) is carriedout as described in Example III.

A 23.2 gram quantity of crude material is recovered and purified in themanner described in Example I to yield 6.0 grams of the pure acid (13%).

Analysis calculated for C₁₃ H₁₉ NO₃ : C, 65.80; H, 8.07; N, 5.90 ;Found: C, 65.66; H, 8.30; N, 5.73

EXAMPLE V Preparation of Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionate ##STR15##

318 milligrams of the hydroxy-acid (Example IV) are converted to thesodium salt by reacting it with sodium bicarbonate as described inExample II. The product is obtained in the form of a white solid inessentially quantitative yield.

EXAMPLE VI Pyrolysis of2-(2-Butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionic acid

A 1.5 gram quantity of the hydroxy-acid described in Example I ispyrolyzed at 250° C. for 8 minutes in a flask equipped with a condenser.

Analysis of the pyrolyzate by preparative thin layer chromatographyindicates that the product mixture contains 810 milligrams (54%) of a1:1 mixture of 3-acetylpyridine and 3-methylvaleric acid.

Also separated by preparative thin layer chromatography are 240milligrams (21.7%) of 1-(3-pyridyl)-1-methyl-2-(2-butyl)ethylene, thestructure of which is confirmed by IR and NMR. The material is distilledat 55° -60° C./0.025 mm Hg. This new compound is characterized bygreen-floral aroma. ##STR16##

Analysis calculated for C₁₂ H₁₇ N: C, 82.23; H, 9.78; N, 7.99; Found: C,82.22; H, 9.75; N, 7.92

EXAMPLE VII Pyrolysis of2-(2-Butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionic acid

A 1.35 gram quantity of the hydroxy-acid described in Example IV ispyrolyzed at 250° C. for 15 minutes in an open test tube.

Analysis of the pyrolysis mixture by preparative thin layerchromatography indicates that the product mixture contains 430milligrams (65%) of 3-methylvaleric acid and 300 milligrams (42.8%) of4-acetylpyridine.

Also separated by preparative thin layer chromatography are 110milligrams (11%) of 1-(4-pyridyl)-1-methyl-2-(2-butyl)ethylene as anoil, the structure of which is confirmed by IR and NMR. This newcompound is characterized by green-floral aroma ##STR17##

Analysis calculated for C₁₂ H₁₇ N: C, 82.23; H, 9.78; N, 7.99; Found: C,82.18; H, 9.99; N, 8.05

EXAMPLE VIII Pyrolysis of 2-(2-Butyl)-3-methyl-3-(2-pyrazyl) propionicacid

A 0.82 gram quantity of the hydroxy-acid described in Example III ispyrolyzed at 250° C. for 15 minutes in an open test tube.

Analysis of the pyrolyzate by preparative thin layer chromatographyindicates that the product mixture contains 120 milligrams (30%) of3-methylvaleric acid and 80 milligrams (19%) of 2-acetylpyrazine.

Also separated by preparative thin layer chromatography are 50milligrams of 1-(2-pyrazyl )-1-methyl-2-(2-butyl)ethylene (8.3%) as anoil, the structure of which is confirmed by IR and NMR. This newcompound is characterized by green-floral aroma. ##STR18##

Analysis calculated for C₁₁ H₁₆ N₂ : C, 74.95; H, 9.15; N, 15.90; Found:C, 75.02; H, 9.14; N, 16.00

EXAMPLE IX Pyrolysis of Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionate

A 1.0 gram quantity of the salt described in Example II is pyrolyzed at250° C. for 8 minutes in an open test tube. The solid product mixture isextracted with methylene chloride and the solvent removed under reducedpressure to give 210 milligrams of 3-acetylpyridine. The remaining solidis dissolved in water and the pH is adjusted to 1.0 with dilute HCl. Thesolution is extracted with methylene chloride, and the organic layer isdried over magnesium sulfate and evaporated to give 280 milligrams of3-methylvaleric acid. No ethylene derivative is detected in thepyrolyzate which differs from the result obtained with the correspondingfree acid pyrolyzate (Example VI)

A similar result is obtained when piperidinium2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionate is pyrolyzed,except that piperidine is a detected product.

Pyrolysis of calcium 2-(2-butyl)-3-methyl-3-(2-pyrazyl)-propionate andammonium 2-(2-butyl)-3-methyl-3-(2-pyrazyl)-propionate, respectively,yield 3-methylvaleric acid and acetylpyrazine, and no detectablequantity of the ethylene derivative.

EXAMPLE X Pyrolysis of Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionate

A 1.0 gram quantity of the salt described in Example V is pyrolyzed andworked up in the manner of Example IX. Analysis of the pyrolyzateindicates that the product mixture contains 160 milligrams of4-acetylpyridine and 130 milligrams of 3-methylvaleric acid.

None of the ethylene derivative described in Example VII is detected inthe pyrolyzate.

A similar result is obtained when dibutylammonium2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionate is pyrolyzed,except that dibutylamine is a detected product.

EXAMPLE XI Pyrolysis of Sodium2-(2-butyl-3-hydroxy-3-methyl-3-(3-pyridyl)propionate Impregnated OnCellulose

A 73 milligram quantity of the salt is dissolved in 2 milliliters ofwater and the solution is used to impregnate 1.15 grams of cellulosefilter paper. The paper is dried at 110° C. for 30 minutes. The paper isshredded and pyrolyzed at 250° C. for 10 minutes in a flask equippedwith a condenser. The residue as well as the distillate obtained areextracted with methylene chloride and the resulting organic solution isdried over magnesium sulfate. Evaporation of the solvent yields 35milligrams of an oil which is mainly a 1:1 mixture of 3-acetylpyridineand 3-methylvaleric acid.

A small amount of the ethylene derivative described in Example VI isalso detected in the product mixture.

EXAMPLE XII Preparation of A Smoking Composition Containing A PresentInvention Flavorant

Cigarettes are fabricated using a typical blend of tobaccos treated withan ethanolic solution of2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionic acid, to provide0.0005 percent of the compound by weight of the tobacco. Untreatedcontrol cigarettes are prepared using the identical tobacco blend, andthe treated cigarettes are compared to the controls by an experiencedsmoking panel. The treated cigarettes are found to have more body andmore response as compared to the controls.

What is claimed is:
 1. A heterocyclic-hydroxy-substituted carboxylicacid composition corresponding to the formula: ##STR19## where X is aheterocyclic substituent containing between about 2-12 carbon atoms, andany heteroatom in X is selected from oxygen, nitrogen and sulfur; R is asubstituent selected from aliphatic, alicyclic and aromatic groupscontaining between about 1-12 carbon atoms; R¹ and R² are hydrogen orsubstituents selected from alilphatic, alicyclic and aromatic groupscontaining between about 1-12 carbon atoms, and R¹ and R² when takentogether with connecting elements form an alicyclic structure; and thecorresponding salts thereof; and wherein one of R¹ and R² is a2-(2-butyl) substituent when X is pyridyl.
 2. A carboxylic acidcomposition in accordance with claim 1 wherein X is a heterocyclicsubstituent selected from pyrazyl and pyridyl radicals corresponding tothe chemical structures: ##STR20## where R³ is a group selected fromhydrogen and lower alkyl groups.
 3. A carboxylic acid composition inaccordance with claim 1 in the form of an alkali metal salt.
 4. Acarboxylic acid composition in accordance with claim 1 in the form of anammonium or organic amine salt. 5.2-(2-Butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionic acid.
 6. Alkalimetal salt of 2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionicacid.
 7. Sodium2-(2-butyl,)-3-hydroxy-3-methyl-3-(3-pyridyl)-propionate.
 8. Ammonium2-(2-butyl)-3-hydroxy-3-methyl-3-(3-pyridyl)propionate. 9.2-(2-Butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionic acid.
 10. Alkalimetal salt of 2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionicacid.
 11. Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)-propionate.
 12. Ammonium2-(2-butyl)-3-hydroxy-3-methyl-3-(4-pyridyl)propionate. 13.2-(2-Butyl)-3-hydroxy-3-methyl-3-(2-pyrazyl)-propionic acid.
 14. Alkalimetal salt of 2-(2-butyl)-3-hydroxy-3-methyl-3-(2-pyrazyl)propionicacid.
 15. Sodium2-(2-butyl)-3-hydroxy-3-methyl-3-(2-pyrazyl)-propionate.
 16. Ammonium2-(2-butyl)-3-hydroxy-3-methyl-3-(2-pyrazyl)propionate.
 17. Aheterocyclic-substituted ethylene composition corresponding to theformula: ##STR21## wherein X¹ is a heterocyclic substituent selectedfrom pyridyl and pyrazyl radicals containing between about 4-12 carbonatoms, and R is a C₁ -C₈ alkyl substituent. 18.1-(3-Pyridyl)-1-methyl-2-(2-butyl)ethylene. 19.1-(4-pyridyl)-1-methyl-2-(2-butyl)ethylene. 20.1-(2-pyrazyl)-1-methyl-2-(2-butyl)ethylene.